CN109078616B - Tannin modified graphene/gelatin porous composite material and preparation method and application thereof - Google Patents
Tannin modified graphene/gelatin porous composite material and preparation method and application thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention belongs to the technical field of dye adsorption materials, and relates to a tannic acid modified graphene/gelatin porous composite material, and a preparation method and application thereof. The tannin modified graphene/gelatin porous composite material is prepared by the method comprising the following steps: 1) mixing tannic acid, graphene oxide and deionized water, reacting at 80-90 ℃, and then carrying out solid-liquid separation to obtain tannic acid modified graphene; 2) mixing the tannic acid modified graphene, gelatin and deionized water to obtain a tannic acid modified graphene/gelatin mixed solution; 3) dripping the tannin modified graphene/gelatin mixed solution into ice water to obtain tannin modified graphene/gelatin microspheres; 4) and (3) carrying out crosslinking reaction on the tannic acid modified graphene/gelatin microspheres and a crosslinking agent, and then carrying out freeze drying to obtain the tannic acid modified graphene/gelatin porous composite material. The tannin modified graphene/gelatin porous composite material disclosed by the invention has a good adsorption effect on organic dyes.
Description
Technical Field
The invention belongs to the technical field of dye adsorption materials, and particularly relates to a tannic acid modified graphene/gelatin porous composite material, a preparation method of the tannic acid modified graphene/gelatin porous composite material and application of the tannic acid modified graphene/gelatin porous composite material as a dye adsorption material.
Background
In recent years, the dye chemical industry in China is rapidly developed and becomes one of the major countries of dye production, consumption and trade in the world. As a chemical raw material, the dye is widely applied to the industries of textile, printing, leather and the like, and is also one of the main sources of water environment pollution, and the discharge amount is increased year by year. The dye has great toxic action on human bodies, obvious pollution on water bodies and difficult degradation in natural environment, so the dye pollution becomes a great problem to be solved urgently in water treatment. Researchers have developed many physical, chemical and biological processes to remove dye residues from wastewater, where adsorption is one of the simple and effective methods.
The graphene material has good adsorption performance due to the high specific surface area, and can be used for sewage treatment; gelatin is a natural water-soluble biodegradable high molecular material, and has the characteristics of low price, rich source and reproducibility. The composite material formed by compounding the graphene and the gelatin has the advantages of both the graphene and the gelatin and is widely concerned. Chinese patent application publication No. CN104275164A discloses a graphene oxide porous composite material for wastewater treatment. The graphene oxide porous composite material comprises the following components in parts by weight: 3-5 parts of graphene oxide, 2-3 parts of layered silicate and 3-5 parts of gelatin. The graphene oxide porous composite material realizes the combination of an inorganic material and an organic material, has good mechanical strength, and has high adsorption capacity on heavy metals in industrial wastewater. But the graphene oxide porous composite material has limited adsorption capacity for organic dyes.
Disclosure of Invention
The invention aims to provide a tannic acid modified graphene/gelatin porous composite material which has a good adsorption effect on organic dyes.
The second purpose of the invention is to provide a preparation method of the tannic acid modified graphene/gelatin porous composite material, and the tannic acid modified graphene/gelatin porous composite material with a better appearance can be prepared by the method.
The third purpose of the invention is to provide an application of the tannic acid modified graphene/gelatin porous composite material as a dye adsorption material, wherein the tannic acid modified graphene/gelatin porous composite material has a good adsorption effect on various organic dyes.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a tannic acid modified graphene/gelatin porous composite material is prepared by the following steps:
1) mixing tannic acid, graphene oxide and deionized water, reacting at 80-90 ℃, and then carrying out solid-liquid separation to obtain tannic acid modified graphene;
2) mixing the tannic acid modified graphene, gelatin and deionized water to obtain a tannic acid modified graphene/gelatin mixed solution;
3) dripping the tannin modified graphene/gelatin mixed solution into ice water to obtain tannin modified graphene/gelatin microspheres;
4) and carrying out crosslinking reaction on the tannic acid modified graphene/gelatin microspheres and a crosslinking agent to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
The step 1) is mixing tannic acid and graphene oxide aqueous solution.
In order to complete the graphene oxide reaction, the tannic acid is in excess. The mass ratio of the tannic acid to the graphene oxide in the step 1) is 1-10: 1.
in order to fully react the tannic acid with the graphene oxide, the reaction time of the tannic acid and the graphene oxide in the step 1) is 4-10 h.
Because the tannin is excessive, solid-liquid separation is carried out after the reaction, and the redundant tannin is removed. And performing solid-liquid separation to obtain a membrane filtration and suction filtration.
The mixing in the step 2) is mixing the tannin modified graphene with a gelatin aqueous solution, wherein the mass content of gelatin in the gelatin aqueous solution is 13-30%. The gelatin is adopted as the matrix of the composite material because the gelatin has the capability of natural degradation and cannot cause pollution to the environment. In addition, the gelatin solution has the capacity of changing into gel at a lower temperature, the modified graphene sheet layer can be coated in the solid gel ball, and the modified graphene composite material and the composite material after dye adsorption are easy to separate from a water body.
The gelatin water solution is prepared by the following method: dispersing gelatin in distilled water, and heating to 50-60 ℃ to dissolve the gelatin to obtain a gelatin water solution.
In the step 2), the mass of the tannic acid modified graphene is 1-8% of that of gelatin, and the coating of the tannic acid modified graphene by the gelatin can be realized.
Dropwise adding the tannin modified graphene/gelatin solution in the step 3) by using an injector or a metering pump, so that the dropwise adding speed can be better mastered.
The dropping speed of the tannic acid modified graphene/gelatin solution in the step 3) is 5-20 drops/min. The gel microspheres with uniform size can be formed at a slower dropping speed.
In order to enhance the strength of the gel microspheres, a cross-linking agent is used to cross-link the gelatin. The crosslinking reaction in the step 4) is a reaction of the tannic acid modified graphene/gelatin microspheres and a crosslinking agent solution, wherein the mass content of the crosslinking agent in the crosslinking agent solution is 0.5-5%.
The cross-linking agent in the step 4) is one of glutaraldehyde and glyoxal. Glutaraldehyde is preferred, and the crosslinking effect is strong.
And 4) carrying out the crosslinking reaction at room temperature for 4-12 h, so that the crosslinking reaction is fully carried out.
According to the tannin modified graphene/gelatin porous composite material, the tannin is used for modifying the graphene oxide, so that part of the graphene oxide can be reduced into reduced graphene, and the adsorption capacity of the reduced graphene on organic dyes is enhanced. Meanwhile, the tannic acid is a hydrophilic substance, so that the binding force between the reduced graphene part and the gelatin can be enhanced. The lamellar structure of the modified graphene enables the composite material to form a three-dimensional porous structure during freeze drying, so that the organic dye is quickly adsorbed.
The tannin modified graphene/gelatin porous composite material disclosed by the invention has the excellent adsorption performance of the modified graphene and the biodegradable characteristic of gelatin. Therefore, the method does not cause secondary pollution to the water quality when the wastewater is treated, and has certain practical application value.
A preparation method of the tannin modified graphene/gelatin porous composite material comprises the following steps:
1) mixing tannic acid, graphene oxide and deionized water, reacting at 80-90 ℃, and then carrying out solid-liquid separation to obtain tannic acid modified graphene;
2) mixing the tannic acid modified graphene, gelatin and deionized water to obtain a tannic acid modified graphene/gelatin mixed solution;
3) dripping the tannin modified graphene/gelatin mixed solution into ice water to obtain tannin modified graphene/gelatin microspheres;
4) and carrying out crosslinking reaction on the tannic acid modified graphene/gelatin microspheres and a crosslinking agent to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
The preparation process of the tannic acid modified graphene/gelatin porous composite material is simple, and raw materials are easy to obtain.
An application of the tannic acid modified graphene/gelatin porous composite material as a dye adsorption material.
The dye is an organic dye. The organic dye includes methylene blue, crystal violet, Congo red and malachite green.
The tannin modified graphene/gelatin porous composite material disclosed by the invention has a good adsorption effect on methylene blue, crystal violet and other organic dyes, and the removal rate is up to more than 90%. The tannin modified graphene/gelatin porous composite material is used as a dye adsorption material, and has a wide practical prospect.
Drawings
Fig. 1 is a composite of example 1 of a tannic acid-modified graphene/gelatin porous composite and a gelatin porous material of a comparative example;
fig. 2 is an SEM image of the composite of example 1 of the tannic acid modified graphene/gelatin porous composite;
in fig. 1, the samples corresponding to the respective reference numerals are: 1-gelatin porous material; 2-tannic acid modified graphene/gelatin porous composite material.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Tannic acid, graphene oxide, gelatin, glutaraldehyde, methylene blue, and the like, referred to in the following examples, are all commercially available products.
Example 1 of preparation method of tannic acid modified graphene/gelatin porous composite
The preparation method of the tannic acid modified graphene/gelatin porous composite material comprises the following steps:
1) mixing 500mg of tannic acid with 500mL of graphene oxide aqueous solution (containing 50mg of GO), reacting for 4h at 80 ℃, filtering through a membrane, and removing unreacted tannic acid to obtain tannic acid modified graphene;
2) putting 5g of gelatin into 20mL of distilled water, and heating to 50 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
3) uniformly dispersing the tannic acid modified graphene into deionized water, then dripping the tannic acid modified graphene into a gelatin solution by using a dropping funnel, and stirring and uniformly mixing to obtain a tannic acid modified graphene/gelatin mixed solution;
4) dripping the tannin modified graphene/gelatin mixed solution into ice water at the speed of 5 drops/min by using an injector to obtain tannin modified graphene/gelatin microspheres;
5) immersing the tannic acid modified graphene/gelatin microspheres into 100mL of glutaraldehyde solution (the mass fraction of glutaraldehyde is 1%), carrying out crosslinking reaction for 12h at room temperature to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then carrying out freeze drying to obtain the tannic acid modified graphene/gelatin porous composite material.
Example 2 of preparation method of tannic acid modified graphene/gelatin porous composite material
The preparation method of the tannic acid modified graphene/gelatin porous composite material comprises the following steps:
1) mixing 100mg of tannic acid and 300mL of graphene oxide aqueous solution (containing 100mgGO), reacting for 6h at 90 ℃, filtering through a membrane, and removing unreacted tannic acid to obtain tannic acid modified graphene;
2) putting 6g of gelatin into 20mL of distilled water, and heating to 50 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
3) uniformly dispersing the tannic acid modified graphene into deionized water, then dripping the tannic acid modified graphene into a gelatin solution by using a dropping funnel, and stirring and uniformly mixing to obtain a tannic acid modified graphene/gelatin mixed solution;
4) dripping the tannin modified graphene/gelatin mixed solution into ice water at the speed of 10 drops/min by using an injector to obtain tannin modified graphene/gelatin microspheres;
5) immersing the tannic acid modified graphene/gelatin microspheres into 100mL of glutaraldehyde solution (the mass fraction of glutaraldehyde is 2.5%), carrying out crosslinking reaction for 4h at room temperature to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
Example 3 of preparation method of tannic acid modified graphene/gelatin porous composite material
The preparation method of the tannic acid modified graphene/gelatin porous composite material comprises the following steps:
1) mixing 200mg of tannic acid and 300mL of graphene oxide aqueous solution (containing 100mgGO), reacting for 8h at 85 ℃, filtering through a membrane, and removing unreacted tannic acid to obtain tannic acid modified graphene;
2) putting 4g of gelatin into 20mL of distilled water, and heating to 60 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
3) uniformly dispersing the tannic acid modified graphene into deionized water, adding the tannic acid modified graphene into a gelatin solution by using a dropping funnel, and stirring and uniformly mixing to obtain a tannic acid modified graphene/gelatin mixed solution;
4) dripping the tannin modified graphene/gelatin mixed solution into ice water at a speed of 15 drops/min by using a metering pump to obtain tannin modified graphene/gelatin microspheres;
5) immersing the tannic acid modified graphene/gelatin microspheres into 80mL of glutaraldehyde solution (the mass fraction of glutaraldehyde is 0.5%), carrying out crosslinking reaction for 8h at room temperature to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
Example 4 of preparation method of tannic acid modified graphene/gelatin porous composite material
The preparation method of the tannic acid modified graphene/gelatin porous composite material comprises the following steps:
1) mixing 600mg of tannic acid with 100mL of graphene oxide aqueous solution (containing 200mgGO), reacting for 10h at 85 ℃, filtering through a membrane, and removing unreacted tannic acid to obtain tannic acid modified graphene;
2) putting 3g of gelatin into 20mL of distilled water, and heating to 50 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
3) uniformly dispersing the tannic acid modified graphene into deionized water, then dripping the tannic acid modified graphene into a gelatin solution by using a dropping funnel, and stirring and uniformly mixing to obtain a tannic acid modified graphene/gelatin mixed solution;
4) dripping the tannin modified graphene/gelatin mixed solution into ice water at the speed of 20 drops/min by using a metering pump to obtain tannin modified graphene/gelatin microspheres;
5) immersing the tannic acid modified graphene/gelatin microspheres into 100mL of glutaraldehyde (the mass fraction of glutaraldehyde is 1.5%) solution, carrying out crosslinking reaction for 8h at room temperature to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
Example 5 of method for preparing tannin modified graphene/gelatin porous composite material
The preparation method of the tannic acid modified graphene/gelatin porous composite material comprises the following steps:
1) mixing 600mg of tannic acid with 300mL of graphene oxide aqueous solution (containing 600mg), reacting for 6h at 85 ℃, filtering through a membrane, and removing unreacted tannic acid to obtain tannic acid modified graphene;
2) putting 8g of gelatin into 20mL of distilled water, and heating to 50 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
3) uniformly dispersing the tannic acid modified graphene into deionized water, then dripping the tannic acid modified graphene into a gelatin solution by using a dropping funnel, and stirring and uniformly mixing to obtain a tannic acid modified graphene/gelatin mixed solution;
4) dripping the tannin modified graphene/gelatin mixed solution into ice water at the speed of 20 drops/min by using a metering pump to obtain tannin modified graphene/gelatin microspheres;
5) immersing the tannic acid modified graphene/gelatin microspheres into 60mL of glutaraldehyde solution (the mass fraction of glutaraldehyde is 5%), carrying out crosslinking reaction for 8h at room temperature to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then carrying out freeze drying to obtain the tannic acid modified graphene/gelatin porous composite material.
Example 1 of tannic acid modified graphene/gelatin porous composite
The tannic acid modified graphene/gelatin porous composite material is prepared by the method of example 1 of the preparation method of the tannic acid modified graphene/gelatin porous composite material.
Example 2 of tannin modified graphene/gelatin porous composite
The tannic acid modified graphene/gelatin porous composite material is prepared by the method of example 2 of the preparation method of the tannic acid modified graphene/gelatin porous composite material.
Example 3 of tannin modified graphene/gelatin porous composite
The tannic acid modified graphene/gelatin porous composite material is prepared by the method of example 3 of the preparation method of the tannic acid modified graphene/gelatin porous composite material.
Example 4 of tannin modified graphene/gelatin porous composite
The tannic acid modified graphene/gelatin porous composite material is prepared by the method of example 4 of the preparation method of the tannic acid modified graphene/gelatin porous composite material.
Example 5 of tannin modified graphene/gelatin porous composite
The tannic acid modified graphene/gelatin porous composite material is prepared by the method of example 5 of the preparation method of the tannic acid modified graphene/gelatin porous composite material.
Comparative example
The gelatin porous material of the present comparative example was prepared by a preparation method comprising the steps of:
1) putting 4g of gelatin into 20mL of distilled water, and heating to 50 ℃ to completely dissolve the gelatin to obtain a gelatin solution;
2) dripping the gelatin solution into ice water at a speed of 15 drops/min by using a medical injector to obtain gelatin microspheres;
3) and (3) immersing the gelatin microspheres into 60mL of glutaraldehyde solution (the mass fraction of glutaraldehyde is 2.5%), carrying out crosslinking reaction for 8h at room temperature to obtain gelatin gel microspheres, and then carrying out freeze drying to obtain the gelatin porous material.
Test examples
The composite materials of examples 1-5 of the tannin modified graphene/gelatin porous composite material and the gelatin porous material of the comparative example were subjected to an adsorption performance test.
The specific test method comprises the following steps: 0.02g of the sample was accurately weighed and added to 10mL of a methylene blue solution having a concentration of 50mg/mL, and then the mixture was put into a water bath constant temperature oscillator (30 ℃ C., 100r/min) and shaken. And measuring the absorbance of the methylene blue solution at the wavelength of 664nm by using an ultraviolet spectrophotometer, and when the absorbance of the solution does not change any more, indicating that the adsorption of the adsorption material on the organic dye reaches adsorption balance. After the adsorption equilibrium is reached, the concentration of the remaining methylene blue is calculated, and the amount of adsorbed methylene blue and the adsorption percentage are obtained. The test results are shown in table 1.
Table 1 adsorption performance test results
| Test sample | Methylene blue adsorption capacity (mg) | Percentage adsorption (%) |
| Example 1 | 22.5 | 90 |
| Example 2 | 22.75 | 91 |
| Example 3 | 23 | 92 |
| Example 4 | 23.5 | 94 |
| Example 5 | 23.75 | 95 |
| Comparative example | 21.5 | 86 |
As can be seen from table 1, the adsorption rate of the tannic acid modified graphene/gelatin porous composite material to methylene blue is above 90%, and the tannic acid modified graphene/gelatin porous composite material has a good adsorption effect.
Claims (10)
1. The tannin modified graphene/gelatin porous composite material is characterized by being prepared by the following steps:
1) mixing tannic acid, graphene oxide and deionized water, reacting at 80-90 ℃, and then carrying out solid-liquid separation to obtain tannic acid modified graphene;
2) mixing the tannic acid modified graphene, gelatin and deionized water to obtain a tannic acid modified graphene/gelatin mixed solution;
3) dripping the tannin modified graphene/gelatin mixed solution into ice water to obtain tannin modified graphene/gelatin microspheres;
4) and carrying out crosslinking reaction on the tannic acid modified graphene/gelatin microspheres and a crosslinking agent to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
2. The tannin modified graphene/gelatin porous composite material of claim 1, wherein: the mass ratio of the tannic acid to the graphene oxide in the step 1) is 1-10: 1.
3. the tannin modified graphene/gelatin porous composite material of claim 1 or 2, wherein: the reaction time in the step 1) is 4-10 h.
4. The tannin modified graphene/gelatin porous composite material of claim 1, wherein: in the step 2), the mixing is carried out by mixing the tannic acid modified graphene with a gelatin aqueous solution, wherein the mass content of gelatin in the gelatin aqueous solution is 13-30%.
5. The tannin modified graphene/gelatin porous composite material of claim 1 or 4, wherein: in the step 2), the mass of the tannic acid modified graphene is 1-8% of that of gelatin.
6. The tannin modified graphene/gelatin porous composite material of claim 1, wherein: the dripping speed of the tannic acid modified graphene/gelatin solution in the step 3) is 5-20 drops/min.
7. The tannin modified graphene/gelatin porous composite material of claim 1, wherein: in the step 4), the crosslinking reaction is a reaction of the tannic acid modified graphene/gelatin microspheres and a crosslinking agent solution, and the mass content of the crosslinking agent in the crosslinking agent solution is 0.5-5%.
8. The tannin modified graphene/gelatin porous composite material of claim 7, wherein: the cross-linking agent in the step 4) is one of glutaraldehyde and glyoxal.
9. A method for preparing the tannin modified graphene/gelatin porous composite material as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
1) mixing tannic acid, graphene oxide and deionized water, reacting at 80-90 ℃, and then carrying out solid-liquid separation to obtain tannic acid modified graphene;
2) mixing the tannic acid modified graphene, gelatin and deionized water to obtain a tannic acid modified graphene/gelatin mixed solution;
3) dripping the tannin modified graphene/gelatin mixed solution into ice water to obtain tannin modified graphene/gelatin microspheres;
4) and carrying out crosslinking reaction on the tannic acid modified graphene/gelatin microspheres and a crosslinking agent to obtain tannic acid modified graphene/gelatin crosslinked gel microspheres, and then freeze-drying to obtain the tannic acid modified graphene/gelatin porous composite material.
10. Use of the tannin modified graphene/gelatin porous composite material of claim 1 as a dye adsorption material.
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